New composition of matter



' Patented Nov.

,UNlTED s rAr s amass I NEW courgsmonor Mama Melvin Dc Groote', St.Louis, and Bernhard Keilei',

Webster Groves, M were to 'lrctolite Company, Webster. Groves, Mo acorporation Jo: Missouri No pplidation December :1, 19:4,

sulfonatable" fatty body and to a method oi pro-' ducing'the same. .Oneobject of our invention is to provide. a 3 new material, composition ofmatter or chemical compound, that is capable, of various industrialuses, but particularly adapted for use as a'raw material in themanufacture of various sultonated ,products intended to be-used for thepurpose for 10 which ordinary Turkey red oils and similar materials areemployed:- Said new material, composition of matter or chemical compoundmay properly be described as a sulfonatable fatty acid, or glyceridesthereof, having less than 16,carb on atoms and more than 5 carbon atomsin the molecule, and derived by the pyrolytic 'or thermal. decompositionor splitting oi? a body obtained by oxidation .of arelatively highlyunsaturated nonhydroxylated fatty body. It is akin to hende whole or itsglycerides and may be considered asisologue or homologue of oic acid orits glycerides.

- Hendecenoic acid or undecylenic acid, as it e sometimes termed, isobtained by distilling recin- -oleic acid or the glyoeride thereof(castor oil) under diminished or atmospheric pressure. .The methodofproducing this acid is well known and is described in the publicationDictionary of Applied Chemistry, by Thorpe, 1922. In volume 4, pages 630and .631 or the said publication, the

reaction of hendecenoic acid is properly indiso but in the text. theterm hendecatoiciacid is erroneously used to refer to the productcannot. However, volume a, page5l5 or the" .atoms. It is understood thatthe expression- "fatty" is here used because the split acid thusobtained is a -lower homologue of ,oleic acid. Ho'wever, so far as weare aware, this acid does not occur naturally in any fat or'oiLas istrue of fatty acids in the usual sense. We will hereinreferto-hendecjenoic acidderived from castdr oil asf'normalhendeoenoic'acid. Y 1 p U. S. Patent No. 1,749,463, to Bertsch, datedMarch .4, 1930 relates to the sulfonation of cer- "tain pyrolytiedecomposition products of caster '55 oil, which ,are'knowmin view or theabovemen- (cur-1n This invention relates toa .new unsaturated,

tioncd publication by Thorpe, consist essen-' tially of hendecenoic acidor a g yceride thereof;

- The valueIof normal hendecenoic acid as a raw material for producingvaluable sulfonated products, is well recognized, in view-ofsa'idBertsch 5 patent. The ability of castor oil or its acid, ricinoleicacid, to undergo thermal or pyrolytic decomposition soas to yield asulfonatable fatty acid or glyceride of lower molecular weight, isunique.- This property does not appear to be en- 10 ioyed by any othercommercially available natural fat or fatty oil. As indicated by thereaction referred to above, it appears that decomposition takes place atthe hydroxyl radical and that the fatty acid or glyceride thereof whichis split air, is

contains the ethylene linkage, and thus is capa-- bio of sulfonation,although presumably the presence of an hydroxyl radical would give thesame effect. The sulfonation of such material is d'escribed not only inthe Bertsch patent previously 9 referred to, but also in our co-pendingapplication for patent Serial No. 760,024, filed December. 31, 1934.

Due to the relatively high cost r oaatoifoii,

and also to the fact that the pyrolytic decomposi- 25 tion reactiohyields an aldehyde and perhaps some hydrocarbon or limitedcommercialvalue, normal 4 hendecenoic acid .is somewhat expensive, andthen even though valuable sulfonated products may be derived therefrom,the cost of the latterismarlr- :ediy higher than the cost of ordinaryTurkey red oils or substitutes therefor. We have attempted toproducematerials similariin chemical proper-. ties to hendecenoic acidor its ester, and in such a manner that t e productss'o obtained willcom- 35 pare favorably in cost with ordinary, fatty materials employedin sulfonation processes, or .for

other purposes, The new composition of matter herein described may beused in the form of an acid, salt or ester to break petroleum emulsionsof the water-in-oil type.'

In producing omnew material or composition 'of matter, weemploy arelatively highly unsaturated fatty body as e raw material. Byrelatively highly unsaturated .body we mean those materials whose iodinenumber is distinctly-high- 'er than 0160 acid, and arethus characterizedas havingamore'than one ethylene linkage present in the hydrocarbon,chain of the characteristic fatty acid'or acids present as such or inthe form of glycerides. It is well known that various dry-' ing andsemi-drying oils, and various marine oils are characterized by an iodinenumber greatly in excess of oleic acid, varying in a general man-.

= pet from approximately to 180 or-190, ton l,

relatively with water to produce two hydroxyl groups.

Whether or not this is the correct explanation, it is known thathydroxyl groups are formed. For

instance, Chemistry of-the Oil Industry",- by

Southcombe, 1926, page 181,'in speaking of blown (oxidized) oils, statesas follows:

"Hydroxyl groups are unquestionably formed, as the considerable rise inacetyl value proves If one uses airor oxygen to blow a fatty materialhaving'a single ethylene linkage, the resultant hydroxylated body has noparticular analogy to ricinoleic acid, but is analogous, perhaps, tohydroxystearic acid. We have found by blowing a hly unsaturated fattyacid or oil of the kind p viously referred to, that the resultantproduct is characterizedby the presence of fatty bodies having both a,hydroxyl radical and an ethylene linkage. I These particular'materialsare analogous to castoroil and may be subjected to thermalor pyrolyticdecomposition in the same manner that castor oil or ricinoleic acid issubradicals, so that the unsaturated acid obtained by pyrolyticdecomposition, may vary in molecular size, depending, in part, upon theposition of the split hydroxyl radical. Thus, one may obtain variousunsaturated acids having a different a number of carbon atoms as aresult of the process ,hereindescribed. In some instances itis evenpossible that the split fatty acids may have a hydroxyl group attachedto the hydrocarbon chain. These split acids appear to be homologues'loor isologues of oleic acid. The lowest homologue of oleic acid which isknown to'occur naturally, appears to be tiglic acid, which has fourcarbon atoms. Lower homologues of oleic acidhaving 6 to 10 atoms appearto be unknown in nattn'al l5 coils. The lower homologue of oleic acid,hende- -cenoic acid, previously referred. to, is obtained mostconveniently by the pyrolytic decomposition of castor oil. Alsohomologues of oleic acid, said to have 12 to 14 carbon atoms, havesometimes 20 been stated to occur in the fat of cochineal;.-

' if this be true, they are only laboratorycm'iosi- .ties' and areunknown commercially or in the trade. We have characterized our newcomposition of matter as containing more than five car'- 25 bon atomsand less than 16 carbon atoms and being derived by the thermal orpyrolyticdecomposition of oxidized '(blown) relatively highlyrmsaturated fatty bodies, so as to clearly define the metes and boundsof our present invention. 30

jected. The resultant product obtained, 1. e., an It is substantiallyfree from or does not containunsaturated fattyacid or glyceride, havingfewer carbon atoms, of course, than the original fatty body from whichit-is derived,is acheap and suitable substitute for hendecenoic acidor'its.

glycerides. Thereis, of course, an aldehyde, such as heptaldehyde(heptoic aldehyde) or somewhat similar bodies formed which may be usedfor the same pin-pose as heptaldehyde. For instance, these aldehydesm'aybe combined with 'bisulfltes,

such as sodium or potassiumbisulfltes, to produce' addition productshaving the-same valuable properties enjoyed by heptaldehyde sodiumblsulflte addition products. For instance, Watts Dictionary of Chemistry(1919) Muirand Morley,- volume 2, page 680, contains the following inre-' to heptoic aldehyde bisulflteaddition prod lution of heptoic'aldehyde containing potash,

soda, or NHs'.--CsH1:.CH(QH-).SO:NA no: brillian't unctuous' scales;vsol.water,v.e.s0l. hot, nearly insol. cold, alcohol."

The alddiydes obtained in the manufacture of our, compositionof-matter,whether composed of' heptoic aldehyde alone or similar materials or amixture, may be employed in the same manner aspureheptoicaldehydetoproduce bisulflte addition products.

It is not intended to infer that the use 'of hendecenoic acid is limitedto its useas a raw niaterial in sulfonation The ammonium We desireto'point-out that the P tics: of the fethylene'linkagesinvarious highlyfatty oils or acids may vary and=that, due to variation in condition ofoxidation, various ethylene'linkages maybe oxidized to produce hydroxylan appreciable amount of hendecenoic acid of the kind obtained fromcastor oil.

Since the bl0wing' (oxidation) of various oils is a welf knowncommercial process, and since the thermal decomposition 0f castor oil isa well known process, it is hardly n to give an elaborate description ofa procedure suitable-for producing our newcompositionof matter, invlewof .what hasbeen said previously as to the .40 sarychemical reactionsinvolved. Briefly stated, a a suitable of selecting 'a suitable,relatively highly oil or acid,-or mixture of the same, blowing saidoil,-

acid or mixture with dry, or prerersf lr. moist 4s air or'with any othersuitable oxidising agent.

-astopsoduceahydroxylatedoroxy material in-whichtherearepresentmbstaneespresentinthesamechamso linkage and then subjecting this oxidised (on)unsaturatedmaterialtopyrolyticorthermaldecomposition in the manneremployed for the then. mail decomposition of eastor oil. The usualprocedimeistoheattoapproximatelyilmtowc u' withalossinweightofnbtover12%.\mderatmospheric ordiminished 0n acoount'oftheirlow0st, and we-particnlarly prefer touse American sardine 'ofltbeealle 00it is frequently available at a cost of.matelyone-halforlessofthecostoloaltoroll. Wem'efertoconducttheblowimproosandthe thermal decomposition intbesamevelehpurely as a matter of convenience. Our preferredcedureinvolvesusingmoripwlbs. oILandbIowingthesame thmoist 'proximately150-to 250 C. untiltliere is iodine number toapproximately originaliodine value, and a rise or vofoxygencorrespondingtothedrop inthe value.Atthecompletion'ofthe blowingprocessfliemoistairisshutofl thetemperatureraisedwimslightlyreduced pressme, so-asto'thermaliy-theoxidised 7;

hydrox'ylradiealandan'etbylenepross acetv v e oil. The aldehyde-likematerials which over, are condensed and employed for any suitablepurpose. The loss in weight of the residue during thermal decompositionshould not exceed, as a rule, or 12% by weight of the original oxidizedsardine oil. The final product which appears to represent homologues orisologues of oleic acid, but not to contain any hendecenoic acid,

may be saponifled in any suitable manner. so as to give salts suitablefor use in the same manner that ammonium salt of normal hendeeenoic acidis employed. As previously indicated, such materials may be employed inresolution of petrolemn emulsions. If desired, the unsaturated materialsobtained, may be sulfonated in the manner described in U. S. patent toBertsch, previously referred to, so as to yield valuable produtts whichmay be employed for various purposes in the same mannerthat Turkeyredoil is employed. It is to be noted that it is immaterial whether thefinal product be an acid or ester, or whether it be converted into a.water-soluble salt, such as the sodium salt; or a water-insoluble salt,such as the calcium salt. It is immaterial whether the raw materialprior to oxidation be an acid, or whether 1 it be a naturally-occurringester, such as sardine oil.

Since the exact decomposition of the materials herein contemplated isnot known, but since they appear to be isologues or homologues ofhendecenoic acid, and exhibit the property of an'ung saturated fattyacid, such as hendecenolc acid,

mal decomposition of a body obtained by oxidation of a relatively highlyunsaturated fatty body; said fatty body, prior to oxidation, beingcharacterinedbyaniodinenumberotnotlessthan and not more than 190, saidoxidation being'conducted at a temperature range of from 1509 C. to 250C.,by means ofairuntii thereisadropintheiodinenumbertoavalueofnotovertwod thirds the original iodine numberand a corresponding increase in the aoetyl value; and said thermaldecomposition being conducted at a temperature range of from 270 C. to330 C., with a loss in weight of not over 12%. 2. A new composition ofmatter, consisting of an unsaturated, saponiflable, fatty acid-materialhaving at least S'carbon atoms and less than 16 carbon-atoms in themolecule and derived by the thermal decomposition of a body obtained by18 oxidation of a relatively highly unsaturated fatty glyceride; saidfatty glyceride, prior to oxidation, being characterized by an iodinenumber of not less than 120 and not more than 190, said oxidation beingconducted at a temperature range $0 of from C. to 250 (2., by means ofair until there is a drop in the iodlnenumber to a'value of not over twothirds the original iodine number and a corresponding increase intheacetyl value; and said thermal decomposition being conducted 25 atatemperature range of from 270 C. to 330 0., with a loss in weight of notover 12%.

3. A new composition of matter, consisting of an unsaturated,saponifiable, fatty acid material having at least 6 carbon atoms andless than is 80 carbon atoms in the molecule and derived by therinaldecomposition of a body obtained by oxidation of sardine oil, saidoxidation being conducted at a temperature range of from 150 C. to 2500., bymeansof air-until thereis adropin iodine number to a value of notover two-thirds the original iodine number and a corresponding increasein the acetyl value; and said thermal decomposition being conducted at atemperature range oi from 270 c. to 330 C., with a loss in weight of notover 12%.

'mvm DEG mm v

